Fungicidal wood protectant compositions

ABSTRACT

A fungicide and process for the protection of wood requiring a mixture of (a) the aluminum salt of N-nitroso-Ncyclohexylhydroxylamine, and (b) Nfluorodichloromethylthiophthalimide or N,N&#39;&#39;-dimethyl-N&#39;&#39;-phenyl(N&#39;&#39;-fluorodichloromethylthio)-sulfamide in a weight ratio of (a): (b) of 1:1 to 8:1, preferably 1:1 to 4:1. This mixture is useful in oily wood protectants or in paints as well as by direct impregnation with a suitable solvent.

United States Patent [191 Pommer et al.

[451 Oct. 7, 1975 FUNGICIDAL WOOD PROTECTANT COMPOSITIONS [75] Inventors: Ernst-Heinrich Pommer,

Limburgerhof; Wolfgang Reuther, Ziegelhausen; Reimer Goettsche, Baden-Baden; Heinrich Poppen, Sinzheim, near Baden-Baden, all of Germany [73] Assignee: BASF Aktiengesellschaft,

Ludwigshafen (Rhine), Germany [22] Filed: July 12, 1974 [21] Appl. No.: 488,001

[30] Foreign Application Priority Data July 17, 1973 Germany 2336290 [52] US. Cl. 424/274; 424/324; 424/325 [51] Int. Cl. A01N 9/20; AOlN 9/22;AO1N 9/24 [58] Field of Search 424/274, 324, 325

[56] References Cited OTHER PUBLICATIONS Chemical Abstracts, 73: P869l7w, (1970). Chemical Abstracts, 62: 3973b, (1965).

Primary ExqminerAlbert T. Meyers Assistant Examiner-Leonard Schenkman Attorney, Agent, or Firm-Johnston, Keil, Thompson & Shurtleff [5 7 ABSTRACT 2 Claims, N0 Drawings FUNGICIDAL WOOD PROTECTANT COMPOSITIONS The present invention relates to a fungicide containing a mixture of different active ingredients.

It is known from German Pat. No. 1,024,743 to use salts of N-nitroso-N-cyclohexylamine (NCl-l) for protecting wood from attack by wood-discoloring fungi such as Pullularia pullulans and Sclerophoma pityophila. However, a disadvantage of this method is that relatively high rates of application are necessary to protect the wood. It is also known to use N-fluorodichloromethylthiophthalimide or N,N-dimethyl-N'- phenyl-( N '-fluorodichloromethylthio )sulfamide to combat wood-discoloring fungi. These substances must also be used in large quantities to achieve adequate protection.

We have now found that a mixture of a. the aluminum salt of NCH and b. N-f1uorodichloromethylthiophthalimide or N,N-

dimethyl-N -phenyl-( N -fluorodichloromethylthio)sulfamide has a fungicidal action which is greater than the action of the individual active ingredients, i.e. the ingredients have a mutual synergistic effect.

These ingredients may be mixed in a wide range ofproportions. For example, a ratio of aluminum salt of NCH to N-fluorodichloromethylthiophthalimide or N,N-dimethyl-N'-phenyl-(N'- fiuorodichloromethylthio)sulfamide of from ,1 :1 to 8:1 and preferably from 2:1 to 4:1, by weight, has been found to give excellent protection from wooddiscoloring fungi. A liquid oil wood protectant applied at the rate of from 100 to 200 cm lm of wood surface may contain up to 4 percent of aluminum salt of NCH and up to 1 fluorodichloromethylthiophthalimide or N,N- dimethyl-N '-phenyl-( N '-fluorodichloromethylthio)sulfamide, by weight. An optimum mixture contains 2 percent of aluminum salt of NCH and 0.5 percent of N-fluorodichloromethylthiophthalimide or N,N-dimethyl-N-phenyl-(N- fluorodichloromethylthio) sulfamide, by weight of the total weight of wood protectant.

The fungicidal mixtures of the invention have, in addition to their fungicidal action, an insecticidal effect with respect to wood-destroying insects. The following wood-discoloring fungi and soft-rot and mold fungi may be controlled with the agents of the invention: Merulius lacrimans, Coniophora cerebella, Lentinus lepideus, Poria vaporaria, Linzites trabea, Paxillus panuoides; Pullularia pullulans, Aspergillus niger, Bispora effusa, Stachybotrys atra, Trichoderma viride, Paecilomyces variotii, Cladosporium herbarum, Sclerophoma pityophila, Chaetomium globosum, Hormiscium spec., Stemphylium spec., Alternaria spec., Phoma violacea.

The mixtures may be used as fungicidally active ingredients of oily wood protectants. They are used for treatment of wood, for example by impregnation or brush application. The mixtures may also be used as fungicides in paints.

EXAMPLE 1 For the purpose of preparing an oily wood protectant containing 2.5 percent of active mixture (ratio 4:1), 0.5 part (all parts are by weight) of N- fluorodichloromethylthiophthalimide or N,N-dimethyl- N'-phenyl-(N'-fluorodichloromethylthio)sulfamide is percent of N- dissolved in 55 parts of a high-aromatics petroleum fraction with slight warming. There are then added 10 parts of an alkyl resin and 2 parts of the aluminum salt of NCl-l and the whole is made up to 100 parts at room temperature with white spirit. Similarly, oily wood protectants are prepared in which the active mixtures have a ratio of 1:1 to 6:1.

In order to prepare water-repellent impregnating paints, water repellents may be added to the oily wood protectant mixtures. Suitable substances are for example zinc's'tearate, aluminum stearate and waxes. The mixtures may be colored by adding inorganic or organic pigments thereto.

For the protection of wood from fungus attack, usually from 50 to 200 ml of the oily wood protectant described in this Example are applied, per m of wood surface, by brush application, spraying or dipping. The method of application used depends for example on whether planed or unplaned wood is to be protected and on the amount of protection required. The amount of active mixture required to protect the wood is, per m of wood surface, from 1 to 10 and preferably from 2 to g and the preferred amount is 2.5 g (ratio 4:1) or 3 g (ratio 2:1 calculated as mixture of solid active ingredients ignoring the contents of solvent, pigment and binder.

The following Example illustrates the very good fungicidal action of the agents of the invention.

EXAMPLE 2 Using a method similar to that described by Butin Verscharfte Mundener Streifenmethode, method of evaluating the anti-blueing properties of oily primers (Farbe und Lack 71, No. 5, pp. 373-374, 1965), the effectiveness of the mixtures described in Example 1 against the blue-staining fungi Sclerophoma pityophila and Pullularia pullulans was tested. Comparative mixtures used were those containing 2 percent of the aluminum salt of NCH or 2 percent of N- fluorodichloromethylthiophthalimide or 2 percent of N,N-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfate used singly. The mixtures were composed of the following ingredients: 1

2 percent-(all percentages are by weight) of aluminum salt of NCl-l or Nfluorodichloromethylthiophthalimide or N,N-dimethyl-N-phenyl(N'- fluorodichloromethylthio)sulfamide,

percent of an oil-modified alkyl resin,

percent of an aliphatics-containing petroleum fraction and 58 percent of an aromatics-containing petroleum fraction.

The control surfaces (no active ingredient applied thereto) were coated with linseed oil varnish.

The tests were carried out on boards of pine sapwood which were treated over one half thereof either with one application of g or 100 g or with two applications of 2 X 100 g of wood protectant mixture. The control surfaces were coated with the same weight of linseed oil varnish. Following application of a colored alkyd resin paint, the boards were weathered for 6 months in the open air and then installed in Kolle culture flasks for examination for fungal attack. At the end of the test period, the control surfaces of the test boards showed blue staining to an extent of percent on average, this being due to the growth of Sclerophoma pityophila and Pullularia pullulans. The results of the tests are listed in the following Table. The effib. N-fluorodichloromethylthiophthalimide or N,N- ciency of the active mixtures and the active ingredients climethyl-N-phenyl-(N- used separately was determined according to the Abbot fluorodichloromethylthio) sulfamide in a weight formula: ratio of (a):(b) of 1:1 to 4:1.

5 2. A process for the protection of wood from fungal damage which comprises treating the wood with a fungicidal amount of a mixture of grown, on Comm minus growth in test a. the aluminum salt of N-nitroso-N-cyclohexylhy- Efficiency in 71 growth on control 100 droxylamine, and

TABLE Mixture Appln. Appln. rate 71 of wood Efiic. of Effic. of Sum of rate of active surface mixture in separate efi'ic's (g/m'-) of ingredients blue-stained 71 active of sep. pinewood (g/rn of ingred. active surface pinewood surface) in '7: ingred A B in 7:

Al salt of NCH (ingred. A) 100 2 2 0 100 84 plus N-fluorodichloro 100 2 l 0 100 73 methylthiophthalimide (ingred. B) 100 2 0.5 78 39 Al salt of NCH (ingred. A) 100 2 75 17 lngred. B 100 2 3O 67 5O 1 4O 56 0.5 70 22 lngred. A A C plus 100 2 2 0 100 92 N.N-dimcthyl-N'-phenyl- 100 7 l 0 100 63 (N '-1luorodichloromethylthio)sulfamide 100 2 0.5 67 (ingred. C) lngred. C 100 2 30 67 50 l 50 44 25 0.5 61) 33 Linseed uil varnish 100 90 with no active ingredients We claim: b. N-fluorodichloromethylthiophthalimide or N,N- 1. A wood protectant composition comprising a fundimethy1-N-phenyl-(N'- gicidal mixture of fluorodichloromethylthio) sulfamide in a weight a. the aluminum salt of N-nitroso-N-cyclohexylhy- 45 ratio of (a):(b) of 1:1 to 4:1.

droxyl-amine, and 

1. A WOOD PROTECTANT COMPOSITION COMPRISING A FUNGICIDAL MIXTURE OF A. THE ALIMINUM SALT OF N-NITROSO-N-CYCLOHEXYLHYDROXYLAMINE AND B. N-FLUORODICHLOROMETHYLTHIOPHTHALIMIDE OR N,N-DIMETHYL-N''-PHENYL-(N-FLUOROICHLOROMETHYLTHIO) SULFAMIDE IN A WEIGHT RATIO OF (A):(B) OF 1:1 TO 4:1.
 2. A process for the protection of wood from fungal damage which comprises treating the wood with a fungicidal amount of a mixture of a. the aluminum salt of N-nitroso-N-cyclohexylhydroxylamine, and b. N-fluorodichloromethylthiophthalimide or N,N-dimethyl-N''-phenyl-(N''-fluorodichloromethylthio) sulfamide in a weight ratio of (a):(b) of 1:1 to 4:1. 